Materials for electronic devices

ABSTRACT

The present application relates to a compound of a formula (I) which contains a spirobifluorene basic structure condensed onto a benzofuran unit. The application furthermore relates to a process for the preparation of the compound of the formula (I), and to the use of the compound of the formula (I) in an electronic device.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 14/911,359, filed Feb. 10, 2016 which is incorporated by referencein its entirety. U.S. application Ser. No. 14/911,359 is a nationalstage application (under 35 U.S.C. § 371) of PCT/EP2014/002031, filedJul. 24, 2014, which claims benefit of European Application No.13004061.1, filed Aug. 15, 2013, both of which are incorporated hereinby reference in their entirety.

The present application relates to a compound having a spirobifluorenebasic structure and a benzofluorene unit condensed onto the latter. Thecompound is suitable for use in electronic devices, in particular inorganic electroluminescent devices (OLEDs).

Electronic devices in the sense of this application are taken to meanso-called organic electronic devices which comprise organicsemiconductor materials as functional materials. In particular, they aretaken to mean OLEDs.

The structure of OLEDs in which organic compounds are employed asfunctional materials is described, for example, in U.S. Pat. Nos.4,539,507, 5,151,629, EP 06768461 and WO 98/27138. In general, the termOLEDs is taken to mean electronic devices which contain one or morelayers comprising organic compounds and emit light on application of anelectrical voltage.

In the case of electronic devices, in particular OLEDs, there isconsiderable interest in an improvement in the performance data, inparticular lifetime, efficiency and operating voltage. An entirelysatisfactory solution has still not been found in these aspects.

The performance data of electronic devices are influenced to a greatextent by layers having a hole-transporting function, such as, forexample, hole-injecting layers, hole-transport layers, electron-blockinglayers and also emitting layers. Novel materials havinghole-transporting properties are continuously being sought for use inthese layers.

It is known from the prior art to employ triarylamines as materialshaving hole-transporting properties in the above-mentioned layers. Thesecan be monotriarylamines, as described, for example, in JP 1995/053955,WO 2006/123667 and JP 2010/222268, or bis- or other oligoamines, asdescribed, for example, in U.S. Pat. No. 7,504,163 or US 2005/0184657.Known examples of triarylamine compounds as materials havinghole-transporting for OLEDs are, inter alia, tris-p-biphenylamine,N,N′-di-1-naphthyl-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) and4,4′,4″-tris-(3-methylphenylphenylamino)triphenylamine (MTDATA).

The prior art furthermore discloses the use of spirobifluorene-arylaminocompounds in OLEDs, inter alia as hole-transport materials (WO2012/034627 and WO 2013/120577).

Also known for this use are spiroblfluorene derivatives which contain abenzofuran unit condensed onto the spirobifluorene basic structure andwhich contain one or more arylamino groups bonded to the spirobifluorenein the 2-position (WO 2013/100467).

In the course of investigations of novel materials for use in OLEDs, ithas now been found, surprisingly, that compounds which contain abenzofuran unit condensed onto a spirobifluorene basic structure andwhich contain an arylamine or carbazole group bonded to thespirobifluorene in a certain position are highly suitable for use inOLEDs, in particular as materials having a hole-transporting function.

The compounds found have one or more properties selected from very goodhole-conducting properties, very good electron-blocking properties, ahigh glass-transition temperature, high oxidation stability, goodsolubility and high temperature stability.

The present invention therefore relates to a compound of the formula (I)

-   -   which contains a group of the formula (B)

bonded to the basic structure of the formula (I) at two adjacentpositions marked by *, where the condensation is such that a bond markedby * in formula (B) in each case links to a position marked by * on thebasic structure of the formula (I);

-   -   which may be substituted by a radical R¹ at one or more        positions on the basic structure of the formula (I) and the        group of the formula (B) which are depicted as unsubstituted;        and    -   which has the following definitions of the variables:

-   A is on each occurrence, identically or differently, a group of the    formula (A1), (A2) or (A3), which is bonded via the bond marked by    #;

-   Ar¹ is on each occurrence, identically or differently, a single bond    or an aromatic or heteroaromatic ring system having 6 to 30 aromatic    ring atoms, which may be substituted by one or more radicals R²;-   Ar² is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 6 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R²;-   X is on each occurrence, identically or differently, a single bond    or a group selected from BR², C(R²)₂, Si(R²)₂, C═O, O, S, S═O, SO₂,    NR², PR² or P(═O)R²;-   R⁰ is on each occurrence, identically or differently, H, D, F, CN,    Si(R³), a straight-chain alkyl or alkoxy group having 1 to 20 C    atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C    atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where    the above-mentioned groups may each be substituted by one or more    radicals R³ and where one or more CH₂ groups in the above-mentioned    groups may be replaced by —R³C═CR³—, —C≡C—, Si(R³)₂, C═O, C═NR³,    —C(═O)O—, —C(═O)NR³—, NR³, P(═O)R³), —O—, —S—, SO or SO₂, or an    aromatic or heteroaromatic aromatic ring system having 5 to 30    aromatic ring atoms, which may be substituted by one or more    radicals R³;-   R¹, R² are on each occurrence, identically or differently, H. D, F,    C(═O)R³, CN, Si(R³)₃, N(Ar³)₂, N(R³)₂, P(═O)(R³)₂, OR³, S(═O)R³,    S(═O)₂R³, a straight-chain alkyl or alkoxy group having 1 to 20 C    atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C    atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where    the above-mentioned groups may each be substituted by one or more    radicals R³ and where one or more CH₂ groups in the above-mentioned    groups may be replaced by —R³C═CR³—, —C≡C—, Si(R³)₂, C═O, C═NR³,    —C(═O)O—, —C(═O)NR³—, NR³, P(═O)R³), —O—, —S—, SO or SO₂, or an    aromatic or heteroaromatic ring system having 5 to 30 aromatic ring    atoms, which may be substituted by one or more radicals R³; two or    more radicals R¹ or R² may be linked to one another and may form a    ring;-   Ar³ is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 5 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R³;-   R³ is on each occurrence, identically or differently, H, D, F,    C(═O)R⁴, CN, Si(R⁴)₃, N(Ar³)₂, N(R⁴)₂, P(═O)(R⁴)₂, OR⁴, S(═O)R⁴,    S(═O)₂R⁴, a straight-chain alkyl or alkoxy group having 1 to 20 C    atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C    atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where    the above-mentioned groups may each be substituted by one or more    radicals R⁴ and where one or more CH₂ groups in the above-mentioned    groups may be replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, C═NR⁴,    —C(═O)O—, —C(═O)NR⁴—, NR⁴, P(═O)(R⁴), —O—, —S—, SO or SO₂, or an    aromatic or heteroaromatic ring system having 5 to 30 aromatic ring    atoms, which may be substituted by one or more radicals R⁴; two or    more radicals R³ may be linked to one another and may form a ring;-   R⁴ is on each occurrence, identically or differently, H, D, F, CN or    an aliphatic, aromatic or heteroaromatic organic radical having 1 to    20 C atoms, in which, in addition, one or more H atoms may be    replaced by D, F or CN; two or more substituents R⁴ may be linked to    one another and may form a ring;-   q is on each occurrence, identically or differently, 0 or 1, where    at least one q in formula (A2) is equal to 1;    i, k, m, n and p are on each occurrence, identically or differently,    0 or 1, where at least one of these indices is equal to 1.

An aryl group in the sense of this Invention contains 6 to 60 aromaticring atoms; a heteroaryl group in the sense of this invention contains 5to 60 aromatic ring atoms, at least one of which is a heteroatom. Theheteroatoms are preferably selected from N, O and S. This represents thebasic definition. If other preferences are indicated in the descriptionof the present invention, for example with respect to the number ofaromatic ring atoms or the heteroatoms present, these apply.

An aryl group or heteroaryl group here is taken to mean either a simplearomatic ring, i.e. benzene, or a simple heteroaromatic ring, forexample pyridine, pyrimidine or thiophene, or a condensed (annellated)aromatic or heteroaromatic polycycle, for example naphthalene,phenanthrene, quinoline or carbazole. A condensed (annellated) aromaticor heteroaromatic polycycle in the sense of the present applicationconsists of two or more simple aromatic or heteroaromatic ringscondensed with one another.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals and which may be linked to the aromatic orheteroaromatic ring system via any desired positions, is taken to mean,in particular, groups derived from benzene, naphthalene, anthracene,phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene,fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene,benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a single bond or by a non-aromatic unit, such as, forexample, one or more optionally substituted C, Si, N, O or S atoms. Thenon-aromatic unit here preferably contains less than 10% of the atomsother than H, based on the total number of atoms other than H in thesystem. Thus, for example, systems such as 9,9′-spirobifluorene,9,9′-diarylfluorene, triarylamine, diaryl ether and stilbene are alsointended to be taken to be aromatic ring systems in the sense of thisinvention, as are systems in which two or more aryl groups areconnected, for example, by a linear or cyclic alkyl, alkenyl or alkynylgroup or by a silyl group. Furthermore, systems in which two or morearyl or heteroaryl groups are linked to one another via single bonds arealso taken to be aromatic or heteroaromatic ring systems in the sense ofthis invention, such as, for example, systems such as biphenyl,terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may in each case also be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from the groups mentioned above under aryl and heteroaryl groupsand from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene,truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole orcombinations of these groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals, ispreferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl,cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl,octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl oroctynyl. An alkoxy or thioalkyl group having 1 to 40 C atoms ispreferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy,i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy,2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy,n-octyloxy, cyclooctyloxy, 2-ethyhexyloxy, pentafluoroethoxy,2,2,2-trifluoroethoxy, methylthio, ethytthio, n-propylthio,i-propyfthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,n-pentylthio, s-pentythio, nhexylthio, cyclohexylthio, n-heptylthio,cycloheptylthio, n-octylthio, cyclooctylthlo, 2-ethylhexylthio,trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio,ethenylthio, propenylthio, butenyithio, pentenylthio, cyclopentenylthio,hexenylthio, cyclohexenylthio, heptenylthlo, cycloheptenylthio,octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio,pentynyithio, hexynylthio, heptynylthio or octynylthio.

The formulation that two or more radicals may form a ring with oneanother is, for the purposes of the present application, intended to betaken to mean, inter alia, that the two radicals are linked to oneanother by a chemical bond. Furthermore, however, the above-mentionedformulation is also intended to be taken to mean that, in the case whereone of the two radicals represents hydrogen, the second radical isbonded at the position to which the hydrogen atom was bonded, withformation of a ring.

A is preferably a group of the formula (A-1) or (A-3), particularlypreferably a group of the formula (A-1).

Ar¹ is preferably selected on each occurrence, identically ordifferently, from a single bond or a divalent group selected frombenzene, biphenyl, terphenyl, fluorene, spirobifluorene, indenofluorene,carbazole, dibenzofuran, dibenzothiophene, each of which is optionallysubstituted by radicals R², or a combination of two or more of thesegroups, but where not more than 30 aromatic ring atoms may be present inAr¹.

Groups Ar¹ are preferably selected from groups of the followingformulae:

where the dashed bonds represent the bonds to the remaining parts offormula (I) and the groups may be substituted by one or more radicals R²at the free positions, but are preferably unsubstituted at the freepositions.

R² in the groups of the formulae (Ar¹-23) and (Ar¹-24) preferablystands, identically or differently, for an alkyl group having 1 to 10 Catoms, in particular for methyl, or a phenyl group, which may besubstituted by one or more radicals R¹ and is preferably unsubstituted.Two alkyl groups R² here may also form a ring with formation of a spirogroup, preferably a cyclohexyl ring or a cyclopentyl ring.

Ar² is preferably selected on each occurrence, identically ordifferently, from an aromatic or heteroaromatic ring system having 6 to25 aromatic ring atoms, which may be substituted by one or more radicalsR². Particular preference is given to phenyl, biphenyl, terphenyl,fluorenyl, spirobifluorenyl, indenofluorenyl, naphthyl, phenanthrenyl,furanyl, benzofuranyl, dlbenzofuranyl, thiophenyl, benzothlophenyl,dibenzothiophenyl, carbazolyl, indolocarbazolyl and indenocarbazolyl,each of which may be substituted by one or more radicals R².

Groups Ar² are preferably selected, identically or differently on eachoccurrence, from groups of the following formulae:

where the dashed bond represents the bond to the nitrogen and the groupsmay be substituted by one or more radicals R² at the free positions, butare preferably unsubstituted at the free positions.

R² in the groups of the formulae (Ar²-88) to (Ar²-82) and (Ar²-85) to(Ar²-87) preferably stands, identically or differently, for an alkylgroup having 1 to 10 C atoms, in particular for methyl, or a phenylgroup, which may be substituted by one or more radicals R³ and ispreferably unsubstituted. Two alkyl groups R² here may also form a ringwith formation of a spiro group, preferably a cyclohexyl ring or acyclopentyl ring.

Preferred embodiments of the groups Ar³ correspond to those for groupsAr².

X is preferably selected on each occurrence, identically or differently,from a single bond or a group selected from C(R²)₂, C═O, O, S and NR². Xis particularly preferably a single bond.

R⁰ is preferably on each occurrence, identically or differently, H, D,F, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R³, or an aromatic or heteroaromatic ring system having 5 to 15aromatic ring atoms. R⁰ is particularly preferably on each occurrence,identically or differently, H, F, a straight-chain alkyl group having 1to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 Catoms, where the above-mentioned groups may each be substituted by oneor more radicals R.

R¹ and R² are preferably on each occurrence, identically or differently,H, D, F, CN, Si(R³)₃, N(R³)₂, a straight-chain alkyl or alkoxy grouphaving 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy grouphaving 3 to 10 C atoms, where the above-mentioned groups may each besubstituted by one or more radicals R³ and where one or more CH₂ groupsin the above-mentioned groups may be replaced by —C≡C—, —R^(s)C═CR³—,Si(R³)₂, C═O, C═NR³, —NR³—, —O—, —S—, —C(═O)O— or —C(═O)NR³—, or anaromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms, which may in each case be substituted by one or more radicals R³,where two or more radicals R¹ or R² may be linked to one another and mayform a ring. R¹ and R² are particularly preferably on each occurrence,identically or differently, H, D, F, CN, a straight-chain alkyl grouphaving 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to10 C atoms, where the above-mentioned groups may each be substituted byone or more radicals R³, or an aromatic or heteroaromatic ring systemhaving 6 to 25 aromatic ring atoms, which may in each case besubstituted by one or more radicals R³.

R¹ is preferably on each occurrence, identically or differently, H, F,CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R³, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R.Particularly preferred groups R¹ are H, F, CN, methyl, tert-butyl,phenyl, biphenyl, dibenzofuran, dibenzothiophene and carbazole.

If a radical R¹ bonded to the basic structure of the formula (I) doesnot represent H, it is preferably bonded in one of positions 4, 5, 4′and 5′ of the spirobifluorene basic structure, where the numbering is asfollows:

R³ is preferably on each occurrence, identically or differently, H, D,F, CN, Si(R⁴)₃, N(Ar³)₂, a straight-chain alkyl or alkoxy group having 1to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to10 C atoms, where the above-mentioned groups may each be substituted byone or more radicals R⁴ and where one or more CH₂ groups in theabove-mentioned groups may be replaced by —C≡C—, —R⁴C═CR⁴—, Si(R⁴)₂,C═O, C═NR⁴, —NR⁴—, —O—, —S—, —C(═O)O— or —C(═O)NR⁴—, or an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁴, where two ormore radicals R³ may be linked to one another and may form a ring. R³ isparticularly preferably on each occurrence, identically or differently,H, D, F, CN, N(Ar³)₂, a straight-chain alkyl group having 1 to 10 Catoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴, or an aromatic or heteroaromatic ring system having 6 to 25aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁴.

p is preferably equal to 1.

k is preferably equal to 1.

n is preferably equal to 0.

Furthermore, the sum of the indices i, k, m, n and p is preferably equalto 1 or 2, particularly preferably equal to 1.

The sum of the indices p and m is preferably equal to 1.

These preferences relating to the indices i, k, m, n and p preferablyoccur in combination with one another.

A preferred embodiment of compounds of the formula (I) corresponding tothe formula (I-A)

where the variables occurring are as defined for formula (I). Thevariables occurring preferably correspond to the embodiments indicatedas preferred above.

A further preferred embodiment of compounds of the formula (I)corresponds to the formula (I-B)

where the variables occurring are as defined for formula (I), with theexception that free positions are not substituted by radicals R¹. R¹ informula (I-B) is preferably selected on each occurrence, identically ordifferently, from H, F, CN, straight-chain alkyl groups having 1 to 10 Catoms or branched or cyclic alkyl groups having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R³, or aromatic or heteroaromatic ring systems having 6 to 25aromatic ring atoms, which may in each case be substituted by one ormore radicals R³, particularly preferably from H, F, CN, methyl,tert-butyl, phenyl, biphenyl, dibenzofuran, dibenzothiophene andcarbazole.

Furthermore, at least one radical R¹ in formula (I-B) is preferablyselected from H, F, CN, straight-chain alkyl groups having 1 to 10 Catoms or branched or cyclic alkyl groups having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R³, or aromatic or heteroaromatic ring systems having 6 to 25aromatic ring atoms, which may in each case be substituted by one ormore radicals R³, particularly preferably from H, F, CN, methyl,tert-butyl, phenyl, biphenyl, dibenzofuran, dibenzothiophene andcarbazole.

The preferred embodiments of the formulae (I-A) and (I-B) preferablyoccur in combination with one another.

R⁰ here is particularly preferably on each occurrence, identically ordifferently, H, D, F, a straight-chain alkyl or alkoxy group having 1 to10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10C atoms, where the above-mentioned groups may each be substituted by oneor more radicals R³. R⁰ here is especially preferably on eachoccurrence, identically or differently, H, F, a straight-chain alkylgroup having 1 to 10 C atoms or a branched or cyclic alkyl group having3 to 10 C atoms, where the above-mentioned groups may each besubstituted by one or more radicals R³.

Preferred embodiments of the compounds of the formula (I) correspond tothe following formulae (I-1) to (I-18):

where the symbols occurring are as defined above.

The preferred embodiments of R⁰, Ar¹ and A, in particular, apply toformulae (I-1) to (I-18).

Particularly preferred embodiments of the compounds of the formulae(I-8) and (I-17) correspond to the formulae (I-8-A) and (I-17-A)

where the symbols occurring are as defined above.

The preferred embodiments of R⁰, Ar¹ and A, in particular, apply toformulae (I-8-A) and (I-17-A).

The following table shows examples of compounds of the formula (I).

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

The compounds of the formula (I) can be synthesised by processes andreaction types known from the prior art, for example halogenation,organometallic addition, Buchwald coupling and Suzuki coupling.

Schemes 1 to 10 show possible synthetic routes for the preparation ofthe compounds according to the invention. They serve to explain theinvention to the person skilled in the art and should not be interpretedas being restrictive. The person skilled in the art will be able tomodify the synthetic routes shown within the bounds of his generalexpert knowledge, or develop completely different routes, if thisappears more advantageous.

Schemes 1 to 8 show processes for the preparation of compounds of theformulae (II-1) to (II-6), which represent intermediates in thepreparation of compounds of the formula (I).

Compounds of the formulae (II-1) to (II-6) have the followingstructures:

each of which may be substituted at one or more free positions by aradical R¹, which is as defined above, and where R⁰ is as defined aboveand the other variables are defined as follows:

-   Z is selected on each occurrence, identically or differently, from    F, Cl, Br, I, B(OR³)₂, OSO₂R³, S(═O)R³ and S(═O)₂R;-   t is on each occurrence, identically or differently, 0 or 1, where    at least one index t per formula is equal to 1.

For the compounds of the formulae (II-1) to (II-6), the definitions ofthe radicals R⁰ and R¹ to R³ indicated above for formula (I) arelikewise regarded as preferred.

For formulae (II-1) to (II-6), it is preferred for precisely one orprecisely two indices t to be equal to 1.

For formulae (II-1) to (II-6), it is preferred for Z to be selected oneach occurrence, identically or differently, from Cl, Br, I and B(OR³)₂.

Of the formulae (II-1) to (II-6), preference is given to the formulae(II-5) and (II-6).

The intermediates of the formulae (II-1) to (II-6) are novel and as suchare a subject-matter of the present application.

In all the following synthesis schemes, the compounds are shownunsubstituted. This does not exclude the presence of any desiredsubstituents in the processes.

Scheme 1 shows a suitable synthesis for the intermediate of the formula(II-6).

Scheme 2 shows a suitable synthesis for the intermediate of the formula(II-5).

Scheme 3 shows a suitable synthesis for the intermediate of the formula(II-4)

Scheme 4 shows a suitable synthesis for the intermediate of the formula(II-3).

Scheme 5 shows a suitable synthesis for the intermediate of the formula(II-1).

Scheme 6 shows a suitable synthesis for the intermediate of the formula(II-2).

Scheme 7 shows a suitable alternative synthesis for intermediates of theformulae (II-1) and (II-4).

Scheme 8 shows a suitable alternative synthesis for intermediates of theformulae (II-2) and (II-3).

The building blocks shown above can be provided with a reactive group,such as, for example, halogen, on the benzofluorene unit, as shown bythe following scheme:

The intermediates of the formulae (II-1) to (II-6) provided withreactive groups Z are versatile building blocks which can be convertedinto compounds of the formula (I), as shown by the following scheme:

The present application therefore also relates to a process for thepreparation of compounds of the formula (I), characterised in thatfirstly the spirobifluorene basic structure is prepared, and, in a laterstep, an arylamino or carbazole group or an aryl or heteroaryl groupwhich is substituted by an arylamino or carbazole group is introducedvia an organometallic coupling reaction.

The organometallic coupling reaction here is preferably a Buchwaldcoupling or a Suzuki coupling.

The compounds described above, in particular compounds which aresubstituted by reactive leaving groups, such as bromine, iodine,chlorine, boronic acid or boronic add ester, can be used as monomers forthe production of corresponding oligomers, dendrimers or polymers.Suitable reactive leaving groups are, for example, bromine, iodine,chlorine, boronic adds, boronic acid esters, amines, alkenyl or alkynylgroups having a terminal C—C double bond or C—C triple bond, oxiranes,oxetanes, groups which undergo a cycloaddition, for example a1,3-dipolar cycloaddition, such as, for example, dienes or azides,carboxylic acid derivatives, alcohols and silanes.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more compounds of the formula (I), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired positions in formula (I) which are substituted by R⁰, R¹ orR². Depending on the linking of the compound of the formula (I) thecompound is a constituent of a side chain of the oligomer or polymer ora constituent of the main chain. An oligomer in the sense of thisinvention is taken to mean a compound which is built up from at leastthree monomer units. A polymer in the sense of the invention is taken tomean a compound which is built up from at least ten monomer units. Thepolymers, oligomers or dendrimers according to the invention may beconjugated, partially conjugated or non-conjugated. The oligomers orpolymers according to the invention may be linear, branched ordendritic. In the structures linked in a linear manner, the units of theformula (I) may be linked directly to one another or they may be linkedto one another via a divalent group, for example via a substituted orunsubstituted alkylene group, via a heteroatom or via a divalentaromatic or heteroaromatic group. In branched and dendritic structures,for example, three or more units of the formula (I) may be linked via atrivalent or polyvalent group, for example via a trivalent or polyvalentaromatic or heteroaromatic group, to form a branched or dendriticoligomer or polymer.

The same preferences as described above for compounds of the formula (I)apply to the recurring units of the formula (I) in oligomers, dendrimersand polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), paraphenylenes (for example in accordance with WO1992/18552), carbazoles (for example in accordance with WO 2004/070772or WO 2004/113468), thiophenes (for example in accordance with EP1028136), dihydrophenanthrenes (for example in accordance with WO2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (forexample in accordance with WO 2004/041901 or WO 2004/113412), ketones(for example in accordance with WO 2005/040302), phenanthrenes (forexample in accordance with WO 2005/104264 or WO 2007/017066) or also aplurality of these units. The polymers, oligomers and dendrimers usuallyalso contain further units, for example emitting (fluorescent orphosphorescent) units, such as, for example, vinyltriarylamines (forexample in accordance with WO 2007/068325) or phosphorescent metalcomplexes (for example in accordance with WO 2006/003000), and/orcharge-transport units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula ((I) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;

(B) YAMAMOTO polymerisation;

(C) STILLE polymerisation; and

(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

For the processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,formulations of the compounds according to the invention are necessary.These formulations can be, for example, solutions, dispersions oremulsions. It may be preferred to use mixtures of two or more solventsfor this purpose. Suitable and preferred solvents are, for example,toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene,tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane,phenoxytoluene, in particular 3-phenoxytoluene, (−)-fenchone,1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene,1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol,2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole,3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene,decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP,p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethyleneglycol butyl methyl ether, triethylene glycol butyl methyl ether,diethylene glycol dibutyl ether, triethylene glycol dimethyl ether,diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether,tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene,pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene,1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these solvents.

The invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or emulsion, comprising at least onecompound of the formula (I) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (I), and at leastone solvent, preferably an organic solvent. The way in which solutionsof this type can be prepared is known to the person skilled in the artand is described, for example, in WO 2002/072714, WO 2003/019694 and theliterature cited therein.

The compounds according to the invention are suitable for use inelectronic devices, in particular in organic electroluminescent devices(OLEDs). Depending on the substitution, the compounds are employed indifferent functions and layers.

The invention therefore furthermore relates to the use of the compoundof the formula (I) in an electronic device. The electronic device hereis preferably selected from the group consisting of organic integratedcircuits (OICs), organic field-effect transistors (OFETs), organicthin-film transistors (OTFTs), organic light-emitting transistors(OLETs), organic solar cells (OSCs), organic optical detectors, organicphotoreceptors, organic field-quench devices (OFQDs), organiclight-emitting electrochemical cells (OLECs), organic laser diodes(O-lasers) and particularly preferably organic electroluminescentdevices (OLEDs).

The invention furthermore relates, as already indicated above, to anelectronic device comprising at least one compound of the formula (I).The electronic device here is preferably selected from the devicesmentioned above.

It is particularly preferably an organic electroluminescent device(OLED) comprising anode, cathode and at least one emitting layer,characterised in that at least one organic layer, which may be anemitting layer, a hole-transport layer or another layer, comprises atleast one compound of the formula (I).

Apart from cathode, anode and the emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, interlayers, charge-generation layers (IDMC2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K.Mori, N. Kawamura, A. Yoko, J. Kido, Multiphoton Organic EL DeviceHaving Charge Generation Layer) and/or organic or inorganic p/njunctions.

The sequence of the layers of the organic electroluminescent devicecomprising the compound of the formula (I) is preferably the following:anode/hole-injection layer/hole-transport layer/optionally furtherhole-transport layer/optionally electron-blocking layer/emittinglayer/electron-transport layer/electron-injection layer/cathode.

However, not all the said layers have to be present, and further layersmay additionally be present.

The organic electroluminescent device according to the invention maycomprise a plurality of emitting layers. These emission layers in thiscase particularly preferably have in total a plurality of emissionmaxima between 380 nm and 750 nm, resulting overall in white emission,i.e. various emitting compounds which are able to fluoresce orphosphoresce and which emit blue or yellow or orange or red light areused in the emitting layers. Particular preference is given tothree-layer systems, i.e. systems having three emitting layers, wherethe three layers exhibit blue, green and orange or red emission (for thebasic structure see, for example, WO 2005/011013). The compoundsaccording to the invention are preferably present in the hole-transportlayer or the electron-blocking layer.

It should be noted that, for the generation of white light, an emittercompound used individually which emits in a broad wavelength range mayalso be suitable instead of a plurality of emitter compounds emitting incolour.

It is preferred in accordance with the invention for the compound of theformula (I) to be employed in an electronic device comprising one ormore emitters. The compound may be present in various layers here,preferably in a hole-transport layer, an electron-blocking layer, ahole-injection layer or in an emitting layer.

The term phosphorescent emitters typically encompasses compounds inwhich the light emission takes place through a spin-forbiddentransition, for example a transition from an excited triplet state or astate having a higher spin quantum number, for example a quintet state.

Suitable phosphorescent emitters (=triplet emitters) are, in particular,compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium,platinum or copper complexes are regarded as phosphorescent emitters.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able, without inventive step, to employ furtherphosphorescent complexes in combination with the compounds of theformula (I) in organic electroluminescent devices. Further examples areshown in a following table.

However, the compound of the formula (I) can also be employed inaccordance with the invention in an electronic device comprising one ormore fluorescent emitters.

In a preferred embodiment of the invention, the compounds of the formula(I) are employed as hole-transport material. The compounds are thenpreferably employed in a hole-transport layer, an electron-blockinglayer or a hole-injection layer.

A hole-transport layer in accordance with the present application is alayer having a hole-transporting function which is located between anodeand emitting layer.

Hole-injection layers and electron-blocking layers in the sense of thepresent invention are taken to be specific embodiments of hole-transportlayers. In the case of a plurality of hole-transport layers betweenanode and emitting layer, a hole-injection layer is a hole-transportlayer which is directly adjacent to the anode or is only separatedtherefrom by a single coating of the anode. In the case of a pluralityof hole-transport layers between anode and emitting layer, anelectron-blocking layer is the hole-transport layer which is directlyadjacent to the emitting layer on the anode side.

If the compound of the formula (I) is employed as hole-transportmaterial in a hole-transport layer, a hole-injection layer or anelectron-blocking layer, the compound can be employed as pure material,i.e. In a proportion of 100%, in the hole-transport layer, or it can beemployed in combination with one or more further compounds. According toa preferred embodiment, the organic layer comprising the compound of theformula (I) then additionally comprises one or more p-dopants. Inaccordance with the present invention, the p-dopants employed arepreferably organic electron-acceptor compounds which are able to oxidiseone or more of the other compounds of the mixture.

Particularly preferred embodiments of p-dopants are the compoundsdisclosed in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP1722602, EP 2045848, DE 102007031220, U.S. Pat. Nos. 8,044,390,8,057,712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US2010/0096600 and WO 2012/095143.

Particularly preferred p-dopants are quinodimethane compounds,azaindenofluorenediones, azaphenalenes, azatriphenylenes, I₂, metalhalides, preferably transition-metal halides, metal oxides, preferablymetal oxides containing at least one transition metal or a metal fromthe 3rd main group, and transition-metal complexes, preferably complexesof Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygenatom as bonding site. The dopants are furthermore preferablytransition-metal oxides, preferably oxides of rhenium, molybdenum andtungsten, particularly preferably Re₂O₇ MoO₃, WO₃ and ReO₃.

The p-dopants are preferably substantially uniformly distributed in thep-doped layers. This can be achieved, for example, by co-evaporation ofthe p-dopant and the hole-transport material matrix.

Preferred p-dopants are, in particular, the following compounds:

In a further preferred embodiment of the invention, the compound of theformula (I) is used as hole-transport material in combination with ahexaazatriphenylene derivative, as described in US 2007/0092755. Thehexaazatriphenylene derivative here is particularly preferably employedin a separate layer.

In a further embodiment of the present invention, the compound of theformula (I) is employed as matrix material in combination with one ormore emitters, preferably phosphorescent emitters.

The proportion of the matrix material in the emitting layer is in thiscase between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5%by vol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the emitter is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of emitters. In this case too,the emitters are generally the compounds whose proportion in the systemis the smaller and the matrix materials are the compounds whoseproportionion in the system is the greater. In individual cases,however, the proportion of an individual matrix material in the systemmay be smaller than the proportion of an individual emitter.

The compounds of the formula (I) are preferably used as a component ofmixed-matrix systems. The mixed-matrix systems preferably comprise twoor three different matrix materials, particularly preferably twodifferent matrix materials. One of the two materials here is preferablya material having hole-transporting properties and the other material isa material having electron-transporting properties. The compound of theformula (I) here is preferably the matrix material havinghole-transporting properties. However, the desired electron-transportingand hole-transporting properties of the mixed-matrix components may alsobe combined principally or completely in a single mixed-matrixcomponents, where the further mixed-matrix component(s) fulfil otherfunctions. The two different matrix materials here may be present in aratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably1:10 to 1:1 and very particularly preferably 1:4 to 1:1. Mixed-matrixsystems are preferably employed in phosphorescent organicelectroluminescent devices. More precise information on mixed-matrixsystems is given, inter alia, in the application WO 2010/108579.

The mixed-matrix systems may comprise one or more emitters, preferablyone or more phosphorescent emitters. In general, mixed-matrix systemsare preferably employed in phosphorescent organic electroluminescentdevices.

Particularly suitable matrix materials which can be used as matrixcomponents of a mixed-matrix system in combination with the compoundsaccording to the invention are selected from the preferred matrixmaterials for phosphorescent emitters indicated below or the preferredmatrix materials for fluorescent emitters, depending on what type ofemitter is employed in the mixed-matrix system.

Preferred phosphorescent emitters for use in mixed-matrix systems arethe phosphorescent emitters shown above.

According to a further preferred embodiment of the invention, thecompound of the formula (I) can be employed as fluorescent emitter in anemitting layer. If the compound according to the invention is employedas fluorescent emitter in an emitting layer, it is preferably employedin combination with one or more matrix materials. Preferred matrixmaterials for use in combination with the compound of the formula (I) asemitter are indicated below.

Preferred embodiments of the various functional materials of theelectronic device are shown below.

Preferred phosphorescent emitters are the above-mentioned compounds andthe compounds shown in the following table:

Preferred fluorescent emitters, besides the compounds of the formula(I), are selected from the class of the arylamines. An arylamine oraromatic amine in the sense of the present invention is taken to mean acompound which contains three substituted or unsubstituted aromatic orheteroaromatic ring systems bonded directly to the nitrogen. At leastone of these aromatic or heteroaromatic ring systems is preferably acondensed ring system, particularly preferably having at least 14aromatic ring atoms. Preferred examples thereof are aromaticanthracenamines, aromatic anthracenediamines, aromatic pyrenamines,aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position. Further preferred emitters are indenofluorenamines orindenofluorenediamines, for example in accordance with WO 2006/108497 orWO 2006/122630, benzoindenofluorenamines or benzoindenofluorenediamines,for example in accordance with WO 2008/006449, anddibenzoindenofluorenamines or dibenzoindenofluorenediamines, for examplein accordance with WO 2007/140847, and the indenofluorene derivativescontaining condensed aryl groups which are disclosed in WO 2010/012328.Preference is likewise given to the pyrenarylamines disclosed in WO2012/048780 and in WO 2013/185871. Preference is likewise given to thebenzoindenofluorenamines disclosed in WO 2014/037077 and thebenzofluorenamines disclosed in EP 13000012.8.

Suitable matrix materials, preferably for fluorescent emitters, arematerials from various classes of substance. Preferred matrix materialsare selected from the classes of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676481 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 2004/081017), thehole-conducting compounds (for example in accordance with WO2004/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO2005/084081 and WO 2005/084082), the atropisomers (for example inaccordance with WO 2006/048268), the boronic acid derivatives (forexample in accordance with WO 2006/117052) or the benzanthracenes (forexample in accordance with WO 2008/145239). Particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising naphthalene, anthracene, benzanthracene and/or pyrene oratropisomers of these compounds, the oligoarylenevinylenes, the ketones,the phosphine oxides and the sulfoxides. Very particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising anthracene, benzanthracene, benzophenanthrene and/or pyreneor atropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another. Preference isfurthermore given to the anthracene derivatives disclosed in WO2006/097208, WO 2006/131192, WO 2007/065550, WO 2007/110129, WO2007/065678, WO 2008/145239, WO 2009/100925, WO 2011/054442 and EP1553154 and the pyrene compounds disclosed in EP 1749809, EP 1905754 andUS 2012/0187826.

Preferred matrix materials for phosphorescent emitters are, besides thecompounds of the formula (I), aromatic ketones, aromatic phosphineoxides or aromatic sulfoxides or sulfones, for example in accordancewith WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680,triarylamines, carbazole derivatives, for example CBP(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO2008/086851, indolocarbazole derivatives, for example in accordance withWO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, forexample in accordance with WO 2010/136109, WO 2011/000455 or WO2013/041176, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2010/015306, WO 2007/063754 or WO2008/056748, zinc complexes, for example in accordance with EP 652273 orWO 2009/062578, diazasilole or tetraazasilole derivatives, for examplein accordance with WO 2010/054729, diazaphosphole derivatives, forexample in accordance with WO 2010/054730, bridged carbazolederivatives, for example in accordance with US 2009/0136779, WO2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080,triphenylene derivatives, for example in accordance with WO 2012/048781,or lactams, for example in accordance with WO 2011/116865 or WO2011/137951.

Suitable charge-transport materials, as can be used in thehole-injection or hole-transport layer or electron-blocking layer or inthe electron-transport layer of the electronic device according to theinvention, besides the compounds of the formula (I), are, for example,the compounds disclosed in Y. Shirota at al., Chem. Rev. 2007, 107(4),953-1010, or other materials as are employed in these layers inaccordance with the prior art.

Materials which can be used for the electron-transport layer are allmaterials as are used in accordance with the prior art aselectron-transport materials in the electron-transport layer.Particularly suitable are aluminium complexes, for example Alq₃,zirconium complexes, for example Zrq₄, lithium complexes, for exampleLiq, benzimidazole derivatives, triazine derivatives, pyrimidinederivatives, pyridine derivatives, pyrazine derivatives, quinoxalinederivatives, quinoline derivatives, oxadiazole derivatives, aromaticketones, lactams, boranes, diazaphosphole derivatives and phosphineoxide derivatives. Furthermore suitable materials are derivatives of theabove-mentioned compounds, as disclosed in JP 2000/053957, WO2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Apart from the compounds of the formula (I), preferred hole-transportmaterials which can be used in a hole-transport, hole-injection orelectron-blocking layer in the electroluminescent device according tothe invention are indenofluorenamine derivatives (for example inaccordance with WO 06/122630 or WO 06/100896), the amine derivativesdisclosed in EP 1661888, hexaazatriphenylene derivatives (for example inaccordance with WO 01/049806), amine derivatives containing condensedaromatic rings (for example in accordance with U.S. Pat. No. 5,061,569),the amine derivatives disclosed in WO 95/09147,monobenzoindenofluorenamines (for example in accordance with WO08/006449), dibenzoindenofluorenamines (for example in accordance withWO 07/140847), spirobifluorenamines (for example in accordance with WO2012/034627 or WO 2013/120577), fluorenamines (for example in accordancewith WO 2014/015937, WO 2014/015938 and WO 2014/015935),spirodibenzopyranamines (for example in accordance with WO 2013/083216)and dihydroacridine derivatives (for example in accordance with WO2012/150001).

The cathode of the electronic device preferably comprises metals havinga low work function, metal alloys or multilayered structures comprisingvarious metals, such as, for example, alkaline-earth metals, alkalimetals, main-group metals or lanthanoids (for example Ca, Bae, Mg, Al,In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkalimetal or alkaline-earth metal and silver, for example an alloycomprising magnesium and sliver. In the case of multilayered structures,further metals which have a relatively high work function, such as, forexample, Ag or Al, can also be used in addition to the said metals, inwhich case combinations of the metals, such as, for example, Ca/Ag,Mg/Ag or Ag/Ag, are generally used. It may also be preferred tointroduce a thin interlayer of a material having a high dielectricconstant between a metallic cathode and the organic semiconductor.Suitable for this purpose are, for example, alkali metal fluorides oralkaline-earth metal fluorides, but also the corresponding oxides orcarbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.).Furthermore, lithium quinolinate (LIQ) can be used for this purpose. Thelayer thickness of this layer is preferably between 0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent or partially transparent in orderto facilitate either irradiation of the organic material (organic solarcells) or the coupling-out of light (OLEDs, O-lasers). Preferred anodematerials here are conductive mixed metal oxides. Particular preferenceis given to indium tin oxide (ITO) or indium zinc oxide (IZO).Preference is furthermore given to conductive, doped organic materials,in particular conductive, doped polymers. Furthermore, the anode mayalso consist of a plurality of layers, for example of an inner layer ofITO and an outer layer of a metal oxide, preferably tungsten oxide,molybdenum oxide or vanadium oxide.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed in order to exclude harmfuleffects of water and air.

In a preferred embodiment, the electronic device according to theinvention is characterised in that one or more layers are applied bymeans of a sublimation process, in which the materials are applied byvapour deposition in vacuum sublimation units at an initial pressure ofless than 10⁻⁵ mbar, preferably less than 10⁻⁵ mbar. However, it is alsopossible here for the initial pressure to be even lower, for exampleless than 10⁻⁷ mbar.

Preference is likewise given to an electronic device, characterised inthat one or more layers are applied by means of the OVPD (organic vapourphase deposition) process or with the aid of carrier-gas sublimation, inwhich the materials are applied at a pressure of between 10 mbar and 1bar. A special case of this process is the OVJP (organic vapour jetprinting) process, in which the materials are applied directly through anozzle and are thus structured (for example M. S. Arnold et al., Appl.Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an electronic device, characterisedin that one or more layers are produced from solution, such as, forexample, by spin coating, or by means of any desired printing process,such as, for example, screen printing, flexographic printing, nozzleprinting or offset printing, but particularly preferably LITI (lightinduced thermal imaging, thermal transfer printing) or ink-jet printing.Soluble compounds of the formula (I) are necessary for this purpose.High solubility can be achieved through suitable substitution of thecompounds.

For the production of an electronic device according to the invention,it is furthermore preferred to apply one or more layers from solutionand one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the formula (I) can be employed in displays, aslight sources in lighting applications and as light sources in medicaland/or cosmetic applications (for example light therapy).

WORKING EXAMPLES A) Synthesis Examples A-1) Example 1: Synthesis ofCompounds (1-1) to (1-13)

Synthesis of 4-(2-bromophenyl)dibenzofuran Int-1

100 g (462 mmol) of dibenzofuran-4-boronic acid, 106 g (439 mmol) of1,2-dibromobenzene and 10.7 g (9.2 mmol) of Pd(Ph₃P)₄ are suspended in980 ml of dioxane. 979 ml of 2 M potassium carbonate solution are slowlyadded to this suspension, and the reaction mixture is heated underreflux for 16 h. After cooling, the organic phase is separated off,filtered through silica gel, washed three times with 200 ml of water andsubsequently evaporated to dryness. The residue is purified bychromatography on silica gel. Yield: 87 g (270 mmol), 58% of theory,purity according to HPLC>98%.

Synthesis of Intermediate Int-7

31 g (90 mmol) of 4-(2-bromophenyl)dibenzofuran are initially introducedin 300 ml of THF at −78° C. 40 ml of BuLi (2 M in hexane) are addeddropwise at this temperature. After 1 hour, 16.9 g (94 mmol) offluoren-9-one in 200 ml of THF are added dropwise. The batch is left tostir overnight at room temperature, added to ice-water and extractedwith dichloromethane. The combined organic phases are washed with waterand dried over sodium sulfate. The solvent is removed in vacuo, and theresidue is, without further purification, heated under reflux at 100° C.overnight with 94 ml of HCl and 1074 ml of AcOH. After cooling, theprecipitated solid is filtered off with suction, washed once with 100 mlof water, three times with 100 ml of ethanol each time and subsequentlyrecrystallised from heptane. Yield: 23.1 g (57 mmol), 58%; purityapprox. 98% according to ¹H-NMR.

The following compounds are prepared analogously to the synthesis ofcompound Int-1 described:

Starting Starting material 1 material 2 Product Yield Int-2

62% Int-3

52% Int-4

55% Int-5

35% Int-6

40% Int-6a

60% Int-6b

65% Int-6c

55% Int-6d

68% Int-6e

60% Int-6f

57% Int-6g

60% Int-6h

65%

The following compounds are prepared analogously to the synthesis ofcompound Int-7 described:

Starting material Starting material 1 2 Product Yield Int-8

80% Int-9

70% Int-10

70% Int-11

79% Int-12

72% Int-13

75% Int-14

80% Int-15

75% Int-16

73% Int-17

70% Int-18

75% Int-19

65% Int-20

58% Int-21

80% Int-22

72% Int-23

75% Int-24

67% Int-24a

75% Int-24b

70% Int-24c

65% Int-24d

75% Int-24e

80% Int-24f

70% Int-24g

65% Int-24h

78% Int-24i

62% Int-24j

65% Int-24k

70% Int-24l

81% Int-24m

75%

Synthesis of Compound (I-1)

11.5 g (31.5 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amineand 14.0 g (28.8 mol) of the bromospiro derivative are dissolved in 320ml of toluene. The solution is degassed and saturated with N₂. 6.8 ml(2.88 mmol) of a 10% tri-tert-butylphosphine solution and 1.32 g (1.44mmol) of Pd₂(dba)₃ are then added, and 9.5 g of sodium tert-butoxide(86.5 mmol) are subsequently added. The reaction mixture is heated atthe boil under a protective atmosphere for 5 h. The mixture issubsequently partitioned between toluene and water, the organic phase iswashed three with water and dried over Na₂SO₄ and evaporated in a rotaryevaporator. After filtration of the crude product through silica gelwith toluene, the residue which remains is recrystallised fromheptane/toluene and finally sublimed in a high vacuum. The purity is99.9% (HPLC). The yield of compound (1-1) is 16.5 g (75% of theory).

Synthesis of Compounds (1-2) to (1-16)

The following compounds are also prepared analogously to the synthesisof compound (1-1) described in Example 1.

Starting Starting material 1 material 2 Product Yield 1-2

78% 1-3

82% 1-4

88% 1-5

67% 1-6

76% 1-7

80% 1-8

78% 1-9

72% 1-10

83% 1-11

75% 1-12

70% 1-13

81% 1-14

65% 1-15

55% 1-16

73%

A-2) Example 2: Synthesis of Compounds (2-2) to (2-4)

15.0 g (36.9 mmol) of the starting compound are dissolved in 150 ml ofacetonitrile, and 5.2 g (29 mmol) of N-bromosuccimide are added inportions at room temperature. When the reaction is complete, water andethyl acetate are added, and the organic phase is separated off, driedand evaporated. The crude product is subsequently washed by stirring anumber of times with hot MeOH/heptane (1:1). Yield: 14.3 g (80%) of thebromospiro derivative Int-25.

The following brominated compounds are prepared analogously:

Brom- Starting inating material 1 reagent Product Yield Int- 26

NBS

78% Int- 27

1) nBuLi, −78° C. 2) BrCH₂— CH₂Br

65% Int- 27a

1) nBuLi, −78° C. 2) I₂

75%

Synthesis of Compounds (2-2) to (2-5)

The following compounds (2-2) to (2-5) are also prepared analogously tothe synthesis of compound (1-1) described in Example 1.

Starting Starting material 1 material 2 Product Yield 2-2

82% [102113-98-4] 2-3

69% 2-4

88% 2-5

50%

A-3) Example 3: Synthesis of Compounds 3-1 to 3-3

20.0 g (40.1 mmol) of bromine derivative, 9.7 g (40.1 mmol) of3-phenyl-9H-carbazole and 24 g of Rb₂CO₃ are suspended in 250 ml ofp-xylene. 0.95 g (4.2 mmol) of Pd(OAc)₂ and 12.6 ml of a 1 Mtri-tert-butylphosphine solution are added to this suspension. Thereaction mixture is heated under reflux for 36 h. After cooling, theorganic phase is separated off, washed three times with 150 ml of waterand subsequently evaporated to dryness. The residue is extracted withhot toluene, recrystallised three times from toluene and finallysublimed in a high vacuum, giving 15.9 g (24.1 mmol), corresponding to60% of theory. The purity is 99.9%.

Synthesis of Compounds (3-2) to (3-4)

The following compounds (3-2) and (3-3) are also prepared analogously tothe synthesis of compound (3-1) described in Example 1.

The following compounds are obtained analogously:

Starting Starting material 1 material 2 Product Yield 3-2

50% 3-3

45%

A-3a) Synthesis of Intermediates for Compounds Under A-4)

30 g (74 mmol) of dibenzospirofluorene are initially introduced in 400ml of THF at −20° C. 49 ml of BuLi (2 M in hexane) are added dropwise atthis temperature. After 4 hours, 33 ml (148 mmol) ofisopropoxytetramethyl-dioxaborolane are added dropwise. The batch isleft to stir overnight at room temperature. When the reaction iscomplete, water and ethyl acetate are added, and the organic phase isseparated off, dried and evaporated. The residue is purified bychromatography on silica gel. Yield: 31 g (59 mmol), 80% of theory,purity according to HPLC>98%.

Starting Borylating material 1 reagent Product Yield Int- 27c

85% Int- 27d

80% Int- 27e

75%

A-4) Example 4: Synthesis of Compounds 4-1 to 4-13

Spirofluoreneboronic Ester Derivative Int-28

50 g (103 mmol) of the bromospirofluorene derivative, 32 g (123 mmol) ofbis(pinacolato)diborane and 309 g (309 mmol) of potassium acetate aresuspended in 800 ml of dioxane. 2.5 g (3.09 mmol) of1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex withDCM are added to this suspension. The reaction mixture is heated underreflux for 16 h. After cooling, the organic phase is separated off,washed three times with 400 ml of water and subsequently evaporated todryness. The residue is recrystallised from toluene (52 g, 95% yield).

The following compounds are prepared analogously:

Starting material 1 Product Yield Int- 29

90% Int- 30

80% Int- 31

88% Int- 32

88% Int- 33

91% Int- 34

85% Int- 34a

80% Int- 34b

85%

Biphenyl-2-ylbiphenyl-4-yl-(4-chlorophenyl)amine Int-35

23.8 g of biphenyl-2-ylbiphenyl-4-ylamine (74 mmol) and 21.2 g of4-chloroiodobenzene (89 mmol) are dissolved in 500 ml of toluene. Thesolution is degassed and saturated with N₂. 3 ml (3 mmol) of a 1 Mtri-tert-butylphosphine solution and 0.33 g (1.48 mmol) of palladium(II)acetate are then added, and 10.7 g of sodium tert-butoxide (111 mmol)are subsequently added. The reaction mixture is heated at the boil undera protective atmosphere for 12 h. The mixture is subsequentlypartitioned between toluene and water, and the organic phase is washedthree times with water and dried over Na₂SO₄ and evaporated in rotaryevaporator. After filtration of the crude product through silica gelwith toluene, the residue which remains is recrystallised fromheptane/toluene. The yield is 29 g (90% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield Int- 36

78% Int- 37

80% Int- 38

81% Int- 39

92% Int- 40

85% Int- 41

75%

Synthesis of Compound (4-1)

24.6 g (46.3 mmol) of spirofluorene pinacoleboronic ester derivative and20.0 g (46.3 mmol) of chlorine derivative are suspended in 300 ml ofdioxane and 14.1 g of caesium fluoride (92.6 mmol). 4.1 g (5.56 mmol) ofbis(tricyclohexylphosphine)palladium dichloride are added to thissuspension, and the reaction mixture is heated under reflux for 24 h.After cooling, the organic phase is separated off, filtered throughsilica gel, washed three times with 100 ml of water and subsequentlyevaporated to dryness. After filtration of the crude product throughsilica gel with toluene, the residue which remains is recrystallisedfrom heptane/toluene and finally sublimed in a high vacuum. The purityis 99.9%. The yield is 29.7 g (80% of theory).

Synthesis of Compounds (4-2) to (4-11) and Int-41a to Int-41c

The following compounds are also prepared analogously to the synthesisof compound (4-1) described in Example 1.

Starting material Starting material 1 2 Product Yield 4-2

78% 4-3

71% 4-4

82% 4-5

89% 4-6

69% 4-7

55% 4-8

63% 4-9

72% 4-10

57% Int-41a

75% Int-41b

80% Int-41c

82% 4-11

50%

A-5) Synthesis of Compounds 5-1 to 5-8 Synthesis of Intermediates Int-42to Int-47

27 g (85 mmol) of bisbiphenylamine and 22.0 g (85 mmol) of1-bromo-fluorenone are dissolved in 170 ml of toluene. The solution isdegassed and saturated with N₂. 4 ml (1.7 mmol) of a 10%tri-tert-butylphosphine solution and 0.2 g (0.89 mmol) of Pd(AcO)₂ arethen added, and 12.2 g of sodium tert-butoxide (127 mmol) aresubsequently added. The reaction mixture is heated at the boll under aprotective atmosphere for 12 h. The mixture is subsequently partitionedbetween toluene and water, and the organic phase is washed three timeswith water and dried over Na₂SO₄ and evaporated in a rotary evaporator.After filtration of the crude product through silica gel with toluene,the residue which remains is recrystallised from heptane/toluene. Thepurity is 99% (NMR). The yield is 34 g (80% of theory).

The following compounds are prepared analogously:

Starting material Starting material 1 2 Product Yield Int- 43

67% Int- 44

75% Int- 45

68% Int- 46

80% Int- 47

78% Int- 48

76%

Synthesis of Compounds 5-1 to 5-8

16 g (51 mmol) of 4-(2-bromophenyl)dibenzofuran are initially introducedin 80 ml THF at −78° C. 13 ml of BuLi (2 M in hexane) are added dropwiseat this temperature. After 1 hour, 24.5 g (47 mmol) of fluoren-9-one in200 ml THF are added dropwise. The batch is left to stir overnight atroom temperature, added to ice-water and extracted with dichloromethane.The combined organic phases are washed with water and dried over sodiumsulfate. The solvent is removed in vacuo, and the residue is, withoutfurther purification, heated under reflux at 100° C. overnight with 94ml of HCl and 1074 ml of AcOH. After cooling, the precipitated solid isfiltered off with suction, washed once with 100 ml of water, three timeswith 100 ml of ethanol each time, recrystallised from heptane andfinally sublimed in a high vacuum. Yield: 8.8 g (12 mmol), 59%; purityapprox. 99.9% according to HPLC.

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield 5-2

55% 5-3

67% 5-4

70% 5-5

49% 5-6

60% 5-7

58% 5-8

65% 5-9

70%

B) Device Examples

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (for examplematerials).

The data of various OLEDs are presented in the following device examplesE1 to E13 and E16 to E18 (inventive examples) and V1 to V4 (comparativeexamples). The substrates used are glass plates coated with structuredITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have inprinciple the following layer structure: substrate/p-dopedhole-transport layer (HIL1)/hole-transport layer (HTL)/p-dopedhole-transport layer (HIL2)/hole-transport layer (EBL)/emission layer(EML)/electron-transport layer (ETL)/electron-injection layer (EIL) andfinally a cathode. The cathode is formed by an aluminium layer with athickness of 100 nm.

The materials required for the production of the OLEDs are shown inTable 1, the various component structures are shown in Table 2.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or the matrix materials in a certainproportion by volume by co-evaporation. An expression such as H1:SEB(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB is present in the layer in aproportion of 5%. Analogously, the electron-transport layer or thehole-Injection layers may also consist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in lm/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltageluminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The term EQE @ 10 mA/cm² denotes the external quantumefficiency at a current density of 10 mA/cm². LT80 @ 60 mA/cm² is thelifetime by which the OLED has dropped to 80% of the initial intensityat a constant current of 60 mA/cm².

TABLE 1 Structures of the materials used

F4TCNQ

HIM

H1

SEB

H2

TEG

ETM

LIQ

NPB

HTMV1

HTM1

HTM2

HTM3

HTM4

HTM5

HTM8

HTM9

HTM10

TABLE 2 Structure of the OLEDs HIL1 HTL HIL2 EBL EML ETL EIL Exp.Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nmThickness/nm Thickness/nm V1 HIM:F4TCNQ(5%) HIM NPB:F4TCNQ(5%) NPBH1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm V2HIM:F4TCNQ(5%) HIM HTMV1:F4TCNQ(5%) HTMV1 H1:SEB1(5%) ETM:LiQ(50%) LiQ20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E1 HIM:F4TCNQ(5%) HIMHTM1:F4TCNQ(5%) HTM1 H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20nm 20 nm 30 nm 1 nm E2 HIM:F4TCNQ(5%) HIM HTM2:F4TCNQ(5%) HTM2H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nmE3 HIM:F4TCNQ(5%) HIM HTM3:F4TCNQ(5%) HTM3 H1:SEB1(5%) ETM:LiQ(50%) LiQ20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E4 HIM:F4TCNQ(5%) HIMHTM4:F4TCNQ(5%) HTM4 H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20nm 20 nm 30 nm 1 nm E5 HIM:F4TCNQ(5%) HIM HTM5:F4TCNQ(5%) HTM5H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nmE6 HIM:F4TCNQ(5%) HIM HTM8:F4TCNQ(5%) HTM8 H1:SEB1(5%) ETM:LiQ(50%) LiQ20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E7 HIM:F4TCNQ(5%) HIMHTM9:F4TCNQ(5%) HTM9 H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20nm 20 nm 30 nm 1 nm E8 HIM:F4TCNQ(5%) HIM HTM10:F4TCNQ(5%) HTM10H1:SEB1(5%) ETM:LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nmV3 HIM:F4TCNQ(5%) HIM NPB:F4TCNQ(5%) NPB H2:TEG(10%) ETM:LiQ(50%) LiQ 20nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm V4 HIM:F4TCNQ(5%) HIMHTMV1:F4TCNQ(5%) HTMV1 H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm20 nm 30 nm 40 nm 1 nm E9 HIM:F4TCNQ(5%) HIM HTM1:F4TCNQ(5%) HTM1H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nmE10 HIM:F4TCNQ(5%) HIM HTM2:F4TCNQ(5%) HTM2 H2:TEG(10%) ETM:LiQ(50%) LiQ20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E11 HIM:F4TCNQ(5%) HIMHTM3:F4TCNQ(5%) HTM3 H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm 20nm 30 nm 40 nm 1 nm E12 HIM:F4TCNQ(5%) HIM HTM4:F4TCNQ(5%) HTM4H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nmE13 HIM:F4TCNQ(5%) HIM HTM5:F4TCNQ(5%) HTM5 H2:TEG(10%) ETM:LiQ(50%) LiQ20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E16 HIM:F4TCNQ(5%) HIMHTM8:F4TCNQ(5%) HTM8 H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm 20nm 30 nm 40 nm 1 nm E17 HIM:F4TCNQ(5%) HIM HTM9:F4TCNQ(5%) HTM9H2:TEG(10%) ETM:LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nmE18 HIM:F4TCNQ(5%) HIM HTM10:F4TCNQ(5%) HTM10 H2:TEG(10%) ETM:LiQ(50%)LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm

Compounds HTM1 to HTM5 and HTM8 to HTM10 according to the invention arevery highly suitable for use as OLED materials, as shown by Examples E1to E13 and E16 to E18 (E1 to E8: singlet components; E9 to E13 and E16to E18: triplet components). Improved performance data of the OLEDs areobtained with the compounds compared with the reference compounds HTMV1and NPB (Comparative Examples V1 and V2: singlet components; V3 and V4:triplet components).

In a singlet blue component, samples E2 (7.9%), E3 (8.6%), E4 (7.9%) andE5 (8.3%) according to the invention exhibit higher quantum efficienciesat 10 mA/cm² compared with reference samples V1 and V2 (6.2% and 7.7%).The lifetime LT80 at 60 mA/cm² in the case of samples E1 (356 h), E2(312 h), E4 (403 h), E6 (275 h), E7 (316 h) and E8 (408 h) according tothe invention is also significantly better than in the case of referencesamples V1 (125 h) and V2 (257 h).

In a triplet green component, reference samples V3 (11.7%) and V4(18.6%) exhibit lower or the same quantum efficiencies at 2 mA/cm² thansamples E10 (18.6%), E12 (19.8%), E16 (19.6%), E17 (19.4%) and E18(18.6%) according to the invention. The lifetimes (80%) at 20 mA/cm² ofsamples E9 (220 h), E10 (96 h), E11 (109 h), E12 (172 h), E13 (111 h),E16 (150 h), E17 (144 h) and E18 (160 h) according to the invention arealso greater than in the case of reference samples V3 (80 h) and V4 (84h).

The invention claimed is:
 1. A compound of the formula, (I-1′), (I-1″),(I-4), (I-7), (I-10), (I-13) or (I-16):

which may be substituted by a radical R¹ at one or more positions on thebasic structure of the formula (I-1′), (I-1″), (I-4), (I-7), (I-10),(I-13) or (I-16) which are depicted as unsubstituted; and which has thefollowing definitions of the variables: A is on each occurrence,identically or differently, a group of the formula (A1), (A2) or (A3),which is bonded via the bond marked by #;

Ar¹ is on each occurrence, identically or differently, a single bond oran aromatic or heteroaromatic ring system having 6 to 30 aromatic ringatoms, which may be substituted by one or more radicals R²; Ar² is oneach occurrence, identically or differently, an aromatic orheteroaromatic ring system having 6 to 30 aromatic ring atoms, which maybe substituted by one or more radicals R²; X is on each occurrence,identically or differently, a single bond or a group selected from BR²,C(R²)₂, Si(R²)₂, C═O, O, S, S═O, SO₂, NR², PR² or P(═O)R²; R⁰ is on eachoccurrence, identically or differently, H, D, F, a straight-chain alkylor alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 10 C atoms where the above-mentioned groups mayeach be substituted by one or more radicals R³ or an aromatic orheteroaromatic ring system having 5 to 15 aromatic ring atoms; R¹ and R²are on each occurrence, identically or differently, H, D, F, CN, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R³, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R³;R³ is on each occurrence, identically or differently, H, D, F, CN, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R⁴, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁴;R⁴ is on each occurrence, identically or differently, H, D, F, CN or analiphatic, aromatic or heteroaromatic organic radical having 1 to 20 Catoms, in which, in addition, one or more H atoms may be replaced by D,F or CN; two or more substituents R⁴ may be linked to one another andmay form a ring; q is on each occurrence, identically or differently, 0or 1, where at least one q in formula (A2) is equal to
 1. 2. Thecompound according to claim 1, wherein A is a group of the formula (A1).3. The compound according to claim 1, wherein X is selected on eachoccurrence, identically or differently, from a single bond or a groupselected from C(R²)₂, C═O, O, S and NR².
 4. The compound according toclaim 1, wherein X is a single bond.
 5. The compound according to claim1, wherein R⁰ is H.
 6. The compound according to claim 1, wherein Ar¹ isa single bond.
 7. The compound according to claim 1, wherein R⁴ is oneach occurrence, identically or differently, H, D, F, CN or analiphatic, aromatic or heteroaromatic organic radical having 1 to 20 Catoms, in which, in addition, one or more H atoms may be replaced by D,F or CN.
 8. The compound according to claim 1, wherein Ar² is selected,identically or differently, from groups of the following formulae

where the dashed bond represents the bond to the nitrogen and the groupsmay be substituted by one or more radicals R² at the free positions. 9.The compound according to claim 1, wherein the compound corresponds toone of formulae below

where the symbols occurring are as defined in claim
 1. 10. The compoundaccording to claim 1, wherein the compound conforms to the followingformula

where Ar¹ is a single bond, A conforms to formula (A1), and R⁰ is H. 11.The compound according to claim 1, wherein R⁰ is H, and Ar¹ is a singlebond, and A conforms to formula (A1), and p=0, n=0, m=0, i=0, and R¹ andR² are on each occurrence, identically or differently, H, D, F, CN, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R³, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R³,and R³ is on each occurrence, identically or differently, H, D, F, CN, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R⁴, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R⁴,and R⁴ is on each occurrence, identically or differently, H, D, F, CN oran aliphatic, aromatic or heteroaromatic organic radical having 1 to 20C atoms, in which, in addition, one or more H atoms may be replaced byD, F or CN.
 12. A compound of one of the formulae (II-1) to (II-6″)

each of which may be substituted at one or more free positions by aradical R¹ R¹ is on each occurrence, identically or differently, H, D,F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branchedor cyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R³, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R³;R⁰ is on each occurrence, identically or differently, H, D, F, astraight-chain alkyl or alkoxy group having 1 to 10 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 10 C atoms wherethe above-mentioned groups may each be substituted by one or moreradicals R³ or an aromatic or heteroaromatic ring system having 5 to 15aromatic ring atoms; R³ is on each occurrence, identically ordifferently, H, D, F, CN, a straight-chain alkyl group having 1 to 10 Catoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴, or an aromatic or heteroaromatic ring system having 6 to 25aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁴; R⁴ is on each occurrence, identically or differently,H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radicalhaving 1 to 20 C atoms, in which, in addition, one or more H atoms maybe replaced by D, F or CN; two or more substituents R⁴ may be linked toone another and may form a ring; Z is selected on each occurrence,identically or differently, from F, Cl, Br, I, B(OR³)₂, OSO₂R³, S(═O)R³and S(═O)₂R³.
 13. A process for the preparation of a compound accordingto claim 1, wherein firstly preparing a spirobifluorene basic structure,and, in a later step, an arylamino or carbazole group or an aryl orheteroaryl group which is substituted by an arylamino or carbazole groupis introduced via an organometallic coupling reaction.
 14. An oligomer,polymer or dendrimer containing one or more compounds according to claim1, where the bond(s) to the polymer, oligomer or dendrimers may belocalised at any desired positions in formula (I) that are substitutedby R⁰, R¹ or R².
 15. A formulation comprising at least one compoundaccording to claim 1 and at least one solvent.
 16. An electronic devicecomprising at least one compound according to claim
 1. 17. Theelectronic device according to claim 16, wherein the device is selectedfrom the group consisting of organic integrated circuits, organicfield-effect transistors, organic thin-film transistors, organiclight-emitting transistors, organic solar cells, organic opticaldetectors, organic photoreceptors, organic field-quench devices, organiclight-emitting electrochemical cells, organic laser diodes and organicelectroluminescent devices.
 18. An organic electroluminescent devicecomprising the compound according to claim 1 is present ashole-transport material or as matrix material of the emitting layer. 19.The compound as claimed in claim 12, wherein the compound is one of theformulae (II-1) to (II-5).
 20. A compound of one of the formula (II-6)

which may be substituted at one or more free positions by a radical R¹,R¹ is on each occurrence, identically or differently, H, D, F, CN, astraight-chain alkyl group having 1 to 10 C atoms or a branched orcyclic alkyl group having 3 to 10 C atoms, where the above-mentionedgroups may each be substituted by one or more radicals R³, or anaromatic or heteroaromatic ring system having 6 to 25 aromatic ringatoms, which may in each case be substituted by one or more radicals R³;R⁰ is on each occurrence, identically or differently, H, D, F, astraight-chain alkyl or alkoxy group having 1 to 10 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 10 C atoms wherethe above-mentioned groups may each be substituted by one or moreradicals R³ or an aromatic or heteroaromatic ring system having 5 to 15aromatic ring atoms; R³ is on each occurrence, identically ordifferently, H, D, F, CN, a straight-chain alkyl group having 1 to 10 Catoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴, or an aromatic or heteroaromatic ring system having 6 to 25aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁴; R⁴ is on each occurrence, identically or differently,H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radicalhaving 1 to 20 C atoms, in which, in addition, one or more H atoms maybe replaced by D, F or CN; two or more substituents R⁴ may be linked toone another and may form a ring; Z is selected on each occurrence,identically or differently, from B(OR³)₂, OSO₂R³, S(═O)R³ and S(═O)₂R³.